Substituted butyl esters of alkyl- and haloalkyl-sulfonic acids

ABSTRACT

Disclosed herein are substituted butyl esters of alkyl- and haloalkyl- sulfonic acids which are useful as herbicides.

United States Patent [1 1 Markley [4 1 Aug. 19, 1975 l l SUBSTITUTEDBUTYL ESTERS OF ALKYL- AND HALOALKYL-SULFONIC ACIDS [75] Inventor:Lowell D. Markley, Midland, Mich.

[52] US. Cl. 260/456 R; 260/456 P; 260/456 A;

260/488 CD; 260/618D; 71/103 [51] Int. Cl. C07c 143/68 [58] Field ofSearch 260/456 R, 456 P; 71/103 [56] References Cited OTHER PUBLICATIONSMitsui et al., Chem. Abstract, 63, 4133f, (1965).

Primary Examiner Bernard l-lelfin Assistant ExaminerNicky Chan Attorney,Agent, or Fir mGary D. Street; Edward E. Schilling 5 7 ABSTRACTDisclosed herein are substituted butyl esters of alkylandhaloalkylsulfonic acids which are useful as herbicides.

30 Claims, N0 Drawings SUBSTITUTED BUTYL ESTERS OF ALKYL- ANDHALOALKYlL-SULFONIC ACIDS SUMMARY OF THE INVENTION The present inventionis directed to novel substituted butyl esters of alkylandhaloalkylsulfonic acids of the following formula:

wherein X represents hydrogen, chloro or methyl; n represents an integerof O to 3, inclusive; R is ringsubstituted in the 3, 4 or 5 ringposition and each R independently represents trifiuoromethyl, alkyl offrom I to about 3 carbon atoms, bromo, chloro, fiuoro, nitro or alkoxyof from I to about 3 carbon atoms; T represents alkyl of from 1 to about18 carbon atoms, haloalkyl of from 1 to about 4 carbon atoms, benzyl,substituted benzyl, phenyl, substituted phenyl or and R and R eachindependently represent hydrogen or alkyl of from I to about 3 carbonatoms.

The compounds of the above Formula I, hereinafter referred to forconvenience as active ingredients, have been found to be active asherbicides in the preand post-emergent control of undesired vegetation.Accordingly, the present invention also encompasses compositionscontaining one or more active ingredients as well as methods ofcontrolling undesired plants. Such methods comprise applying aherbicidally effective amount of one or more active ingredients to thelocus of the undesired plants, that is, the seeds, foliage or other partof the growing plants or soil in which the plants are growing or wouldgrow.

DETAILED DESCRIPTION The term alkyl as used herein and in the appendedclaims is employed to designate a straightor branchedchain radicalcontaining, where not otherwise expressly defined, from 1 to about 18carbon atoms, such as, for example, methyl. ethyl, propyl, isopropyl,butyl, tertbutyl, pentyl, hexyl, heptyl, octyl, nonyl decyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl and the like including thevarious homologues and isomers of alkyl having from 1 to about 18 carbonatoms. The term halo as employed herein means bromo, chloro or iodo. Theterm halo alkyl is employed herein to designate groups such as, forexample, chloromethyl, iodomethyl, bromomethyl, chloroethyl, bromoethyl,iodoethyl, trichloromethyl, dibromethyl, tribromomethyl, di-iodoethyl,chloro-n-propyl, bromon-propyl, isodoisopropyl, bromo-tert-butyl, 1,3,3-trichlorobutyl, l,3,3--tribromobutyl and the like. As

used herein the term alkoxy can be methoxy, ethoxy, npropoxy andisopropoxy. The substituted phenyl and substituted benzyl terms asemployed herein refer to phenyl or benzyl radicals substituted by one ormore, preferably from one to about three, nitro groups, halo groups oralkyl groups of from 1 to about 4 carbon atoms.

The term herbicide is used herein to mean an active ingredient whichcontrols or modifies the growth of plants. By a growth-controlling orherbicidally effective amount is meant an amount of active ingredientwhich causes a modifying effect and includes deviations from naturaldevelopment, such as, for example, killing, retardation, defoliation,desiccation, regulation, stunting, tillering stimulation, dwarfing andthe like. The term plants is meant to include germinant seeds, emergingseedlings and established vegetation, including the roots andabove-ground portions thereof.

The active ingredients of the present invention are usually obtained ascrystalline solids which are soluble in many organic solvents commonlyemployed as herbicidal carriers. The active ingredients of the presentinvention are suitable for use as herbicides, especially as pre-emergentherbicides. Certain of the active ingredients have been found to beparticularly useful as selective herbicides in the presence of desiredstanding or seeded crops. The active ingredients of Formula I wherein nis O constitute a preferred embodiment of the present invention. Anotherpreferred class of active ingredients are those of Formula I wherein nis l. A further preferred embodiment includes active ingredients ofFormula I wherein n is 2. Active ingredients of Formula I wherein n is 3constitute still another preferred embodiment. In other preferredembodiments, T represents alkyl and n represents the integer 0, l, 2 or3, respectively. Active ingredients of Formula I wherein X is chloro andn is the integer 0, l, 2 or 3, respectively, constitute furtherpreferred embodiments of the invention.

In still another preferred embodiment, T is haloalkyl, further preferredare active ingredients wherein T is haloalkyl and n is 0. Furtherpreferred embodiments include active ingredients wherein T is selectedfrom the group consisting of phenyl, substituted-phenyl, benzyl andsubstituted-benzyl and n is O, l, 2 or 3, respectively. In suchpreceding embodiments, phenyl and substituted-phenyl are especiallypreferred. In additional preferred embodiments, T represents and nrepresents the integer O, l, 2 or 3, respectively. Especially preferredembodiments of the present invention include those respective activeingredients wherein X is chloro, n is l, R is halo and is substituted inthe 3- ring position and wherein X is chloro, n is 2, R is halo and suchR groups are substituted in the 3, 5ring positions. Other especiallypreferred embodiments include those respective active ingredients ofFormula I wherein X is chloro, n is l, R is alkyl and is substituted inthe 3-ring position and those wherein X is chloro, n is 2, R is alkyland said R groups are substituted in the 3,5-ring positions.Particularly preferred embodiments include those respective activeingredients wherein T is alkyl, X is chloro, n is l or 2, R is bromo,chloro, fluoro or alkyl and is respectively substituted in the 3- or3,5- ring positions.

The active ingredients of the present invention are prepared by reactinga selected substituted phenyl -2 hydroxybutanol reactant with a selectedsubstituted sulfonyl halide reactant. The reaction, which is ordinarilycarried out in the presence of an inert carrier medium, can beschematically illustrated as follows:

The X, R, n and T substituents in the above formulas are as previouslydefined. The hydrogen chloride liberated during the reaction is removedby use of binding agents such as triethylamine, calcium carbonate andthe like. Generally, equimolar amounts of the reactants and bindingagent are employed. Representative carrier media include, for example,those such as acetone, benzene, methylene chloride, chloroform or thelike.

In carrying out the reaction, the substituted phenyl l 2-butanediolreactant is mixed with the carrier medium and the binding agent addedthereto. The resulting mixture is cooled in an ice-alcohol bath to atemperature below about C., generally from about 0 to about -C., and asolution of the substituted sulfonyl halide reactant in a portion of thecarrier medium is added dropwise thereto. The reaction mixture isagitated and the temperature is maintained below about 0C. during theaddition. Following the completion of the sulfonyl halide reactantaddition, the reaction mixture is allowed to warm to ambienttemperatures. The reaction mixture is subsequently washed with water,then with a 10% solution of sodium carbonate, and again with water. Theorganic product layer is separated and the same is dried over sodiumsulfate, filtered, and the reaction mixture volume is reduced byremoving most or all of the carrier medium present in vacuo. Theresulting solid product residue is recovered and can be further purifiedby recrystallization from a solvent, such as tetrachloroethylene or oneof those mentioned herein before. Where the product residue is an oil,the same can be treated with a benzenehexane mixture to crys tallize theproduct.

The following examples illustrate the present invention and the mannerby which it can be practiced but, as such, are not to be construed aslimitations upon the overall scope of the same.

EXAMPLE 1 4,4,4-Trichloro-2-phenyl-2-hydroxybutanol 160 grams; 0.60mole) was mixed with about 2,000 milliliters (m1.) of methylene chlorideand triethylamine (63.6 grams; 0.63 mole) was added thereto. The resulting mixture was cooled in an ice-methanol bath to a temperature of about6 to about 8C. Methanesulwas washed with water (four 700 ml. portions),then with 700 ml. of a 10% sodium carbonate solution, and finally withanother 700 ml. portion of water. An addi tional 600 ml. of methylenechloride was added to the organic product layer which was then driedover sodium sulfate. The volume of the organic product mixture wasreduced to about 400 ml. by evaporation of the carrier medium in vacuo.The resulting white product precipitate was obtained by filtration. As aresult of such operations, the desired 4,4,4-trichloro-2-phenyl-Z-hydroxybutyl l-methane-sulfonate product was obtained as a whitecrystalline solid having a melting point of 128130C.

EXAMPLE 2 4,4,4-Trichloro-2-( 3 ,5-dichlorophcnyl )-2- hydroxybutanol(5.2 grams, 0.015 mole) was dissolved in ml. of methylene chloride andtriethylamine 1.61 gram; 0.016 mole) added thereto. The resultingmixture was cooled in an ice-methanol bath to below about 0C. and asolution of methane-sulfonyl chloride (1.83 gram; 0.016 mole) in 25 ml.of methylene choride was added dropwise thereto. Following thecompletion of the methane-sulfonyl addition, the reaction mixture wasstirred at ambient temperatures for a period of about 16 hours and thendiluted with ml. of methylene chloride and washed successively withwater (2100 m1. portions), 100 ml. of a 10% Na CO solution and another100 ml. of water. The organic product layer was dried over sodiumsulfate and the carrier medium was removed in vacuo, leaving an oilyresidue. The oily residue was mixed with a benzene-hexane mixture togive the desired product as white solid, which was subsequentlyrecrystallized twice from a benzenehexane mixture. As a result of suchoperations, the desired 4,4,4-trichloro-2-( 3 ,5-dichlorophenyl )-2-hydroxybutyl l-methanesulfonatc product was obtained as a white solidhaving a melting point of 99l04C.

Other active ingredients of the present invention are similarly preparedby employing procedures analogous to those set forth in the aboveexamples and the foregoing teachings of the specification by reacting aselected 4,4-dichloro-2-(3,4,5-trichlorophenyl)-2- hydroxypentylethylsulfamate;

4,4-dichloro-2 (3,5-bis(trifluoromethyl)-phenyl-2- hydroxybutyldiisopropylsulfamate;

4,4,4-trichlor-2-( 3 ,5-dibromo-4-methylphenyl )-2- hydroxybutylsulfamate;

4,4-dichloro-2-(3,5-dinitrophenyl)-2-hydroxybutyl sulfamate;

4,4-dichloro-2-(3,5-diisopropylphenyl)-2- hydroxypentyl methylsulfamate;

4,4,4-trichloro-2-( 3 ,5-dimethyl-4-(trifluoromethyl)phenyl)-2-hydroxybutyl ethylsulfamate;

4,4-dichloro-2-(3-methyl-5-nitrophenyl)-2- hydroxypentyldiethylsulfamate;

4,4,4-trichloro-2-( 5-chloro-3-methyl-4-nitrophenyl Z-hydroxybutyldimethylsulfamate;

4,4-dichloro-2-(4-trifluoromethyl hydroxybutyl methylsulfamate;

4,4-dichloro-2-( 3-methoxyphenyl )-2-hydroxypentyl sulfamate;

4,4,4-trichloro-2-(3-chloro-5-methoxyphenyl)-2- hydroxybutylmethylsulfamate;

4,4-dichloro-2-(3,5-dipropoxyphenyl)-2- hydroxybutyl n-propylsulfamate;and

4,4,4-trichloro-2-( 3bromo-5-( trifluoromethyl) phenyl)-2-hydroxybutylsulfamate.

The compounds of the present invention have been found to be suitablefor use in methods for the pre-and post-emergent control of weeds orother unwanted vegetation. Certain of the active ingredients of thepresent invention have been found to be active against undesiredvegetation in the presence of desired crop plants while giving little orno herbicidal action on the crop plants. For all such uses, unmodifiedactive ingredients of the present invention can be employed. However,the present invention embraces the use of a herbicidally effectiveamount of the active ingredients in composition form with an inertmaterial known in the art as an adjuvant or carrier in solid or liquidform. Thus, for example, an active ingredient can be dispersed on afinely divided solid and employed therein as a dust. Also, the activeingredients, as liquid concentrates or solid compositions comprising oneor more of the ac tive ingredients, can be dispersed in water, typicallywith the aid of a wetting agent, and the resulting aqueous dispersionemployed as a spray. In other procedures, the active ingredient can beemployed as a con stituent of organic liquid compositions, oil-in-Waterand water-in-oil emulsions, or water dispersions, with or without theaddition of wetting, dispersing, or emulsifying agents.

Suitable adjuvants of the foregoing type are well known to those skilledin the art. The methods of applying the solid or liquid herbicidalformulations similarly are well known to the skilled artisan.

As organic solvents used as extending agents there can be employedhydrocarbons, e.g., benzene, toluene, xylene, kerosene, diesel fuel,fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethylketone and cyclohexanone, chlorinated hydrocarbons such as carbontetrachloride, chloroform, trichloroethylene, and perchloroethylene,esters such as ethyl acetate, amyl acetate and butyl acetate, ethers,e.g., ethylene glycol monomethyl ether and diethylene glycol monomethylether, alcohols, e.g., methanol, ethanol, isopropanol, amyl alcohol,ethylene glycol, propylene glycol, butyl Carbitol acetate and glycerine.Mixtures of water phenyl)-2- and organic solvents, either as solutionsor emulsions, can be employed.

The active ingredients can also be applied as aerosols, e.g., bydispersing them by means of a compressed gas such asdichlorodifluoromethane or trichlorofluoromethane and other Freons andGenetrons, for example.

The active ingredients of the present invention can also be applied withsolid adjuvants or carriers such as talc, pyrophyllite, synthetic finesilica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheatflour, soybean flour, pumice, tripoli, wood flour, walnut shell flour,redwood flour and lignin.

As stated, it is frequently desirable to incorporate a surface activeagent in the compositions of the present invention. Such surface activeor wetting agents are advantageously employed in both the solid andliquid compositions. The surface active agent can be anionic, cationicor nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long chain mercaptans andalkylene oxides. Typical examples of such surface active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkylphenol ethylene oxide condensation products, e.g.,pisooctylphenol condensed with 10 ethylene oxide units, soaps, e.g.,sodium stearate and potassium oleate, sodium salt of propylnaphthalenesulfonic acid, di(2- ethylhexyl)-ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decane sulfonate, sodium salt of thesulfonated monoglyceride of coconut fatty acids, sorbitan sesquioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether, polyethylene glycol estersof fatty acids and rosin acids, e.g., Ethofat 7 and 13, sodiumN-methyl-N-oleyl taurate, Turkey Red Oil, sodium dibutyl naphthalenesulfonate, sodium lignin sulfonate, polyethylene glycol stearate, sodiumdodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether(nonionic 218), long chain ethylene oxidepropylene oxide condensationproducts, e.g., Pluronic 61 (molecular weight 1000), polyethylene glycolester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate,tris(polyoxyethylene)-sorbitan monostearate (Tween 60), and sodiumdihexyl sulfosuccinate.

The concentration of the active ingredients in solid or liquidcompositions generally is from about 0.003 to about percent by weight ormore. Concentrations of from about 0.003 to about 50 weight percent areoften employed. In compositions to be employed as concentrates, theactive ingredient can be present in a concentration of from about 5 toabout 98 weight percent. The active ingredient compositions can alsocontain other compatible additaments, for example, phytotoxicants, plantgrowth regulants, pesticides and the like and can be formulated withsolid particulate fertilizer carriers such as ammonium nitrate, urea andthe like.

The present compositions can be applied by the use of power-dusters,boom and hand sprayers, spraydusters, by addition to irrigation water,and by other conventional means. The compositions can also be appliedfrom airplanes as a dust or a spray since certain of the activeingredients are effective at low application rates.

The exact rate to be applied is dependent not only upon the specificactive ingredient being employed, but also upon the particular plantspecies to be modified and the stage of growth thereof as well as thepart of the plant to be contacted with the toxic active ingredient.Thus, it is to be understood that all of the active ingredients of theinvention and compositions containing the same may not be equallyeffective at similar concentrations or against the same plant species.In non-selective pre-emergence and foliage treatments, the activeingreclients of this invention are usually applied at an approximaterate of from about 1 to about 25 lbs. per acre, but lower or higherrates may be appropriate in some cases. In selective pre-emergenceoperations to foliage, a dosage of from about 0.13 to about 4.0 poundsper acre is usually employed but higher dosages may be necessary in someinstances. In view of the foregoing and following disclosures, oneskilled in the art can readily determine the optimum rate to be appliedin any particular case.

So as to illustrate the general and selective herbicidal properties ofthe active ingredients of the present invention, a group of controlledgreenhouse experiments is described below.

EXAMPLE 3 Various species of plants were planted in beds of goodagricultural soil in a greenhouse. After the plants had emerged andgrown to a height of about 2-6 inches, certain of the plants weresprayed with a given volume of a solution containing 4000 parts permillion of the candidate active ingredient, prepared by mixing theselected active ingredient and emulsifier or dispersant with water.Sufficient volumes of the solutions were applied to provideapproximately 10.0 pounds of active ingredient per acre. Other plantswere left untreated to serve as controls.

After a period of approximately 14 days, the effect of each of the testingredients on the plants was evaluated by a comparison with the controlgroup of plants.

In such operations, each of the 4,4,4-trichloro-2 phenyI-Z-hydroxybutyll-methanesulfonate (Compound A), 4,4,4-trichloro-2-phenyl-2-hydroxybutyll-benzenesulfonate (Compound B), 4,4,4-trichloro-2-phenyI-Z-hydroxybutyl l-(4-methylbenzene)sulfonate (Compound C),4,4,4-trichloro-2-hydroxy-2- phenylbutyl l-hexadecanesulfonate (CompoundD) and 4,4,4-trichloro-2-phenyl-2-hydroxybutyll-(4-nitrobenzene)sulfonate (Compound E) test ingre dients was found togive from 70 to 100 percent control of the growth of crabgrass, Johnsongrass, barnyard grass and wild oats. In the same operations, each of the4,4,4-trichloro-2-phenyl-2-hydroxybutyl 1- methylsulfamatc (Compound F),4,4,4-trichloro-2- phenyl-Z-hydroxybutyl l-(3-chloropropane)sulfonate(Compound G), 4,4,4-trichloro-2-(3-chlorophenyl)-2- hydroxybutyll-methanesulfonate (Compound H) and 4,4,4-trichloro-2-(3,5-dichlorophenyl )-2-hydroxybutyl l-methanesulfonate (Compound 1)active ingredients was found to give from 70 to 100 percent control ofthe growth of crabgrass, barnyard grass, wild oats and yellow foxtailwhile each of the 4,4,4-trichloro-2-hydroxy- 2-phenylbutyll-butanesulfonate (Compound J), 4,4,4- trichloro-2-hydroxy2-phenylbutyl2-propanesulfonate (Compound K), and 4,4,4-trichloro-2-hydroxy-2-phenylbutyl l-(1-methylethyl)sulfonate (Compound L) active ingredientswas found to give from to percent control of the growth of crabgrass andyellow foxtail. Further, in such operations, each of Compounds A, C, E,F, G and H were found to be sustantially non-phytotoxic to cottonplants.

EXAMPLE 4 In representative pre-emergence operations, seeds of selectedweed species are planted in seedbeds and, while exposed, sprayed withcompositions containing an active test ingredient. The seeds are thancovered with a layer of soil and the test beds maintained underconditions conducive to growth for a period of about 14 days. The testcompositions are prepared as set forth hereinbefore. In suchrepresentative operations, each of Compounds A, B, C, D, E, G and J asset forth in Example 3 above and each of the active ingredients 4,4,4-trichloro-2-hydroxy-2-phenylbutyl 1-( 4-bromobenzene)sulfonate (CompoundM), 4,4,4-trichloro-2- hydroxy2-phenylbutyl 1 -benzenemethanesulfonate(Compound N), 4,4,4-trichloro-2-hydroxy-2- phenylbutyl sulfamate(Compound 0) and 4,4,4- trichloro-2hydroxy-2-phenylbutyl ethanesulfonatewas found to give from 70 to 100% control of germination and growth ofcrabgrass, Johnson grass and barnyard grass seeds at an application rateof 1 pound per acre. None of the foregoing compounds was found toproduce any significant phytotoxic effects on the germina tion andgrowth of cotton seeds. Compounds F, H, I and K from Example 3 abovesimilarly were found to give from 70 to 100 percent control of thegrowth of crabgrass, barnyard grass, wild oat and yellow foxtail seedsat an application rate of ten pounds per acre; Compounds F and Iexhibited no significant phytotoxic effects on the growth of cottonseeds at such application rate.

Certain of the above and other active ingredients of the presentinvention are also active against some or all of the above plant speciesand other plant species, such as, for example, pigweed, quackgrass,nutsedge, giant foxtail, bindweed and the like at various applicationrates. Certain of the active ingredients of the present invention alsoexhibit selective phytotoxic action against undesired vegetation in thepresence of seeded or standing crops such as, for example, soybeans andcorn.

The substituted sulfonyl halide reactants of Formula III which areemployed as starting materials in the preparation of the activeingredients of the present inven tion are known and are eithercommercially available or can be readily prepared by those skilled inthe art according to methods set forth or analogous to those set forthin the open literature. The substituted 2-phenyl-2- hydroxybutanolreactants of Formula II can be readily obtained according to thefollowing general reaction sequence:

C--CH. .(Cl X OH I 40% CH CO H CH;,COCH CCH CCI X Stop (a) ll I OH cricocmccn cci x HOCH CCH CCI X 0 CH3OH Step (b) cn cocr-l,

wherein X, R and n are as previously defined. 25 layer of the resultingmixture was separated therefrom,

Step (a) of the reaction is usually carried out by mixing Reactant Awith glacial acetic acid and adding concentrated sulfuric acid and theperacetic acid thereto. The resulting reaction mixture is usually heatedat temperatures of from about 25 to about 65C. for a period of fromabout 50 to about 100 hours. Generally, an excess amount of theperacetic acid is employed. The course of the reaction is monitored bydetermining the presence of peroxide present in the reaction mixture.Following the reaction period, the reaction mixture is diluted withwater and a solvent, such as, for example, methylene chloride, and theorganic layer is separated, washed with water and neturalized with abase, e.g., sodium carbonate and the like and dried over sodium sulfate.The solvent present in the mixture is removed in vacuo and the resultingresidue, representing reactant (B), is mixed with methanol and a smallamount of p-toluenesulfonic acid. The resulting mixture is refluxed fora period of from about 4 to about 24 hours, cooled, and mixed with waterand methylene chloride. The organic layer is separated from theresulting mixture, washed with water and dried over sodium sulfate. Thesolvent is removed in vacuo to obtain a product residue representingreactant (II).

In veiw of the foregoing and the following specific representativeexample, the necessary starting materials of Formula H can be readilyprepared by those skilled in the art.

EXAMPLE 5 a-(2,2,2-trichloroethyl)-3,5-dichlorostyrene (10.0 grams,0.033 mole) was mixed with 75 ml. of glacial acetic acid and drops ofconcentrated sulfuric acid and 16.5 ml. of 40% peracetic acid were addedthereto. The resulting reaction mixture was heated at about 60C., withstirring, for a period of about 72 hours. The reaction mixture wassubsequently diluted with 200 ml. of water and 200 ml. of methylenechloride. The organic layer of the resulting mixture was separated andwashed successively with 2-100 ml. portions of water, 2l00 ml. portionsof a 10% sodium carbonate solution, 100 ml. portion of a 5% sodiumbisulfite solution and another 100 ml. portion of water. The organicdried over sodium sulfate and the solvent removed in vacuo. The residualoil thus obtained was dissolved in about ml. of methanol and 0.3 gram ofp-toluenesulfonic acid were added thereto. The resulting mixture washeated under reflux conditions for a period of about 11 hours and thencooled and diluted with 200 ml. of water and 200 ml. of methylenechloride. The organic layer of the resulting mixture was separated,dried over sodium sulfate. The solvent was removed in vacuo to obtainthe desired 4,4,4-trichloro-2-(3,5- dichlorophenyl)-2-hydroxybutanolproduct as a clear oily liquid.

What is claimed is:

l. A compound of the formula wherein n represents an integer of 0 to 3,inclusive; R is substituted in the 3, 4 or 5 positions and each Rindependently represents trifluoromethyl, alkyl of from I to about 3carbon atoms, bromo, chloro, fluoro, nitro or alkoxy of from 1 to about3 carbon atoms; and T represents alkyl of from 1 to about 18 carbonatoms or haloalkyl of from 1 to about 4 carbon atoms.

2. The compound according to claim 1 where n is 0.

3. The compound according to claim 1 where n is l.

4. The compound according to claim 1 where n is 2.

5. The compound according to claim 1 where n is 3.

6. The compound according to claim 3 wherein R is bromo, chloro orfluoro and is substituted in the 3 position.

7. The compound according to claim 3 wherein R is alkyl and issubstituted in the 3-ring position.

8. The compound according to claim 4 wherein each R is bromo, chloro orfluoro, said R groups being substituted in the 3, positions.

9. The compound according to claim 4 wherein each R is alkyl, said Rgroups being substituted in the 3, 5 positions.

10. The compound according to claim 1 wherein T is alkyl.

11. The compound according to claim 2 wherein T is alkyl.

12. The compound according to claim 3 wherein T is alkyl.

13. The compound according to claim 4 wherein T is alkyl.

14. The compound according to claim 5 wherein T is alkyl.

15. The compound according to claim 11 which is 4,-4,4-trichloro-2-phenyl-2-hydroxybutyl lmethanesulfonate.

16. The compound according to claim 11 which is 4,-

4,4-trichloro-2-hydroxy-2-phenylbutyl l-hexadecanesulfonate.

17. The compound according to claim 11 which is 4,-4,4trichloro-2-hydroxy-2-phenybutyl lhutanesulfonate.

18. The compound according to claim 11 which is 4,-4,4-trichloro-2-hydroxy-2-phenylbutyl 2-propanesulfonate.

19. The compound according to claim 11 which is 4,-

4,4-trichloro-Z-hydroxy-Z-phenylbutyl ate ethanesulfon- 20. The compoundaccording to claim 11 which is 4,-

4,4-trichloro-2-hydroxy-2-phenylbutyl thyl )-sulfonate.

l-( l-methyle- 21. The compound according to calim 1 wherein T ishaloalkyl.

22. The compound according to claim 2 wherein T is haloalkyl.

23. The compound according to claim 21 which is 4,-

4,4-trichloro-2-hydroxy-2-phenylbutyl propane )-sulfonate.

l-( 3-chloro- 24. The compound according to claim 6 wherein T is alkyl.

25. The compound according to claim 7 wherein T is alkyl.

26. The compound according to claim 8 wherein T is alkyl.

27. The compound according to claim 9 wherein T is alkyl.

methanesulfonate.

29. The compound according to claim 24 which is 4,- 4,4-trichlor0-2-(3-chlorophenyl )-2hydroxybutyl 1- methanesulfonate.

30. The compound according to claim 26 which is 4,- 4,4-trichloro2-( 3,S-dichlorophenyl )-2-hydroxybutyl l-methanesulfonate.

1. A COMPOUND OF THE FORMULA
 2. The compound according to claim 1 where n is
 0. 3. The compound according to claim 1 where n is
 1. 4. The compound according to claim 1 where n is
 2. 5. The compound according to claim 1 where n is
 3. 6. The compound according to claim 3 wherein R is bromo, chloro or fluoro and is substituted in the 3 position.
 7. The compound according to claim 3 wherein R is alkyl and is substituted in the 3-ring position.
 8. The compound according to claim 4 wherein each R is bromo, chloro or fluoro, said R groups being substituted in the 3, 5 positions.
 9. The compound according to claim 4 wherein each R is alkyl, said R groups being substituted in the 3, 5 positions.
 10. The compound according to claim 1 wherein T is alkyl.
 11. The compound according to claim 2 wherein T is alkyl.
 12. The compound according to claim 3 wherein T is alkyl.
 13. The compound according to claim 4 wherein T is alkyl.
 14. The compound according to claim 5 wherein T is alkyl.
 15. The compound according to claim 11 which is 4,4,4-trichloro-2-phenyl-2-hydroxybutyl 1-methanesulfonate.
 16. The compound according to claim 11 which is 4,4,4-trichloro-2-hydroxy-2-phenylbutyl 1-hexadecanesulfonate.
 17. The coMpound according to claim 11 which is 4,4,4-trichloro-2-hydroxy-2-phenybutyl 1-butanesulfonate.
 18. The compound according to claim 11 which is 4,4,4-trichloro-2-hydroxy-2-phenylbutyl 2-propanesulfonate.
 19. The compound according to claim 11 which is 4,4,4-trichloro-2-hydroxy-2-phenylbutyl ethanesulfonate.
 20. The compound according to claim 11 which is 4,4,4-trichloro-2-hydroxy-2-phenylbutyl 1-(1-methylethyl)-sulfonate.
 21. The compound according to calim 1 wherein T is haloalkyl.
 22. The compound according to claim 2 wherein T is haloalkyl.
 23. The compound according to claim 21 which is 4,4,4-trichloro-2-hydroxy-2-phenylbutyl 1-(3-chloropropane)-sulfonate.
 24. The compound according to claim 6 wherein T is alkyl.
 25. The compound according to claim 7 wherein T is alkyl.
 26. The compound according to claim 8 wherein T is alkyl.
 27. The compound according to claim 9 wherein T is alkyl.
 28. The compound according to claim 27 which is 4,4,4-trichloro-2-(3,5-dimethylphenyl)-2-hydroxybutyl methanesulfonate.
 29. The compound according to claim 24 which is 4,4,4-trichloro-2-(3-chlorophenyl)-2-hydroxybutyl 1-methanesulfonate.
 30. The compound according to claim 26 which is 4,4,4-trichloro-2-(3,5-dichlorophenyl)-2-hydroxybutyl 1-methanesulfonate. 